Impact of regulated and emerging pollutants and microplastics in marine ecosystems (IMPACTA project)

Marine ecosystems are nowadays subjected to a massive input of synthetic chemicals from everywhere. Unfortunately only a small portion of them is being monitored, and it is necessary to identify which pollutants can produce adverse impacts in the marine environment. IMPACTA project (CTM2013-48194-C3) is characterizing the distribution of regulated and emerging contaminants and microplastics in marine sediments, and evaluating the biological effects that they can cause (sing sublethal embryotoxicity tests, endocrine disruption and biomarkers). Sensitive and selective analytical methods are being developed and validated for pharmaceuticals, perfluorinated compounds, organophosphorus pesticides, triazines, personal care products, nonylphenols and alkylated PAHs in sediments. Thus, relevant pollutants present in coastal and offshore areas will be identified. Furthermore potential toxic effects of the contaminants present in coastal sediments are being assessed through embryotoxicity bioassays and also the biological effects on different marine species as a consequence of their exposition to specific compounds. Another relevant contribution of this project will be the assessment of the impact of micro-plastics, first time in the Spanish coastal areas. Their potential toxic effects and their role in the transference of pollutants in the marine environment are being assessed. The concentration and composition of microplastics in sediments and demersal fish stomachs are being characterized, and their potential biological effects on marine invertebrates are also being investigated

Time to Switch to Second-line Antiretroviral Therapy in Children With Human Immunodeficiency Virus in Europe and Thailand.

Background: Data on durability of first-line antiretroviral therapy (ART) in children with human immunodeficiency virus (HIV) are limited. We assessed time to switch to second-line therapy in 16 European countries and Thailand. Methods: Children aged <18 years initiating combination ART (≥2 nucleoside reverse transcriptase inhibitors [NRTIs] plus nonnucleoside reverse transcriptase inhibitor [NNRTI] or boosted protease inhibitor [PI]) were included. Switch to second-line was defined as (i) change across drug class (PI to NNRTI or vice versa) or within PI class plus change of ≥1 NRTI; (ii) change from single to dual PI; or (iii) addition of a new drug class. Cumulative incidence of switch was calculated with death and loss to follow-up as competing risks. Results: Of 3668 children included, median age at ART initiation was 6.1 (interquartile range (IQR), 1.7-10.5) years. Initial regimens were 32% PI based, 34% nevirapine (NVP) based, and 33% efavirenz based. Median duration of follow-up was 5.4 (IQR, 2.9-8.3) years. Cumulative incidence of switch at 5 years was 21% (95% confidence interval, 20%-23%), with significant regional variations. Median time to switch was 30 (IQR, 16-58) months; two-thirds of switches were related to treatment failure. In multivariable analysis, older age, severe immunosuppression and higher viral load (VL) at ART start, and NVP-based initial regimens were associated with increased risk of switch. Conclusions: One in 5 children switched to a second-line regimen by 5 years of ART, with two-thirds failure related. Advanced HIV, older age, and NVP-based regimens were associated with increased risk of switch

((R)-(-)-3-Hydroxyquinuclidium)[FeCl4]; A Plastic Hybrid Compound with Chirality, Ferroelectricity and Long Range Magnetic Ordering

Quinuclidinium salts and their derivatives are now in the focus of materials science as building units of multifunctional materials. Their properties can be easily switchable, allowing their use in a wide range of physical applications. One type of these kinds of materials, the homochiral hybrid halometallate ferroelectric compounds, is not well understood. In this work, (R)-(-)-3-quinuclidinol hydrochloride was used in the synthesis of ((R)-(-)-3-hydroxyquinuclidium)[FeCl4]. The use of this enantiomeric cation forces crystallographic non-centrosymmetry, which was confirmed by polarimetry and circular dichroism spectroscopy. We studied the physical properties of this compound at different temperatures by single crystal, synchrotron and neutron powder X-ray diffraction, which showed a rich series of structural and magnetic phase transitions. From synchrotron powder X-ray diffraction data, a plastic phase was observed above 370 K (phase I). Between 370 K and ca. 310 K, an intermediate polar phase was detected, solved in a non-centrosymmetric polar space group (C2) (phase II). Below ca. 310 K, the compound crystallizes in the triclinic P1 non-centrosymmetric space group (phase III) which is maintained down to 4 K, followed by phase IV, which shows tridimensional magnetic ordering. The temperature evolution of the neutron diffraction data shows the appearance of new reflections below 4 K. These reflections can be indexed to a commensurate propagation vector k = (0, 0, ½). The magnetic structure below TN was solved in the Ps1 Shubnikov space group, which gives rise to an antiferromagnetic structure, compatible with the magnetometry measurements. Near room temperature, the crystal phase transition is associated with a dielectric change. In particular, the phase transition between phase III (S.G.:P1) and phase II (S.G.:C2) involves an increase of symmetry between two non-centrosymmetric space groups. Therefore, it allows, by symmetry, the emergence of ferroelectric and ferroelastic ordering. Piezoresponse force microscopy (PFM) imaging measurements provided evidence for polarization switching and a local ferroelectric behavior of phase III at room temperature. Additionally, the obtained butterfly curve and hysteresis loop by PFM exhibits a low coercive voltage of ∼10 V. This value is remarkable, since it approaches those obtained for materials with application in ferroelectric random access memories (FeRAMs).Universidad País Vasco GIU17/50, PPG17/37Ministerio de Economía y Competitividad MAT2017-89239-C2-(1,2)-P, MAT2017-83631-C3-3-R, MAT2017-86453-R, PGC2018-097520-A-100, PID2019-104050RA-I0